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Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy |
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| Authors: | Rachel L. Meyer Samuel M. Greer Anastasia V. Blake Samantha K. Cary Alexander S. Ditter Scott R. Daly Feng Li Stosh A. Kozimor Ellen M. Matson Veronika Mocko Gerald T. Seidler Benjamin W. Stein Samuel D. Weinstein |
| Affiliation: | 1. Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545 USA Department of Chemistry, University of Rochester, Rochester, NY, 14627 USA;2. Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545 USA;3. Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545 USA Department of Chemistry, University of Iowa, Iowa City, IA, 52242 USA;4. Department of Chemistry, University of Iowa, Iowa City, IA, 52242 USA;5. Department of Chemistry, University of Rochester, Rochester, NY, 14627 USA;6. Department of Physics, University of Washington, Seattle, WA, 98195-1560 USA |
| Abstract: | A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron-functionalized and hexavanadium polyoxovanadate-alkoxide clusters, which we characterized here using V K-edge X-ray absorption spectroscopy. Substantial changes in the pre-edge peak intensities were observed that tracked with the V 3d-electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the FeIII cations were electronically isolated from the polyoxovanadate core. |
| Keywords: | iron mixed-valent compounds polyoxometalates vanadium X-ray absorption spectroscopy |